Hydroxy-alkyl ethers of 4-tertiaryalkyl phenols



' Patented 16, 1939.

' HTDBOXY-ALKYL ETHEBS" F 4-TEBTIABY- 1 ALKYL PHENOLS Gerald B. Coleman and John W. Zomba, Midland, Mich, asaixnors to The Dow Chemical Company, Midland, Mieln, a corporation of Michigan NoDrawing. Application February 23, 1937. Serial N0. 127,177

11 Claims. (Cuzco-61s) This invention concerns hydroxy-alkyl ethers of phenol compounds having a formula:

5 (points-0 11 Y I Y wherein one R represents hydrogen or the methyl radical, the other R represents hydrogen, X rep- 15 resents a tertiary-alkyl radical, and each Y represents an alkyl, chloro-, or bromo-radical, or hydrogen. 4

We have prepared members of this class of compounds, determined certain physical characteristics thereof whereby they. may be readily identified, and found that they are particularly useful in the preparation of compositions for the control of household insect pests, such as fly sprays.

25 These new compounds may be prepared by reacting a suitable phenol compound with an halohydrin, e. g. ethylene bromohydrin, propylenechlorohydrin, etc., in the presence of a suitable alkali, e. g. NaOH, KOH, etc.

30 In preparing bur new compounds, the phenol may be dissolved in aqueous alkali and the halohydrin added thereto at a reaction temperature with stirring. If desired, however, the reaction may be carried out by first mixing the phenol with the halo-hydrin and subsequently adding theretothe alkali. While any suitable quantities of reactants may be employed, good yields of the desired products can be obtained when equimo- -lecular proportions of reactants are. used. The

4 reaction may be conveniently carried out at the refluxing temperature of the mixture, but lower or higher temperatures may be employed. In certain cases where the reactants are not readily soluble in aqueous alkali, alcohol. or other water 5 miscible organic solvent may be added to the reaction mixture. Following completion of the reaction the mixture is allowed to stand and separate into layers, the oily layer being subsequently separated, and the desired compound isolated 50 therefrom by fractional distillation under reduced pressure or otherwise.

Other methods by which the compounds may be prepared are: (1) the condensation of the alkylene oxides with suitable ring-substituted phenols, and (2) the etherification of the dihydroxy paraflin hydrocarbons with the tertiaryalkyl substituted phenols.

The following examples describe the preparation of certain representative members of our new group of compounds, but are not to be con- 6 strued as limiting the invention:

Example 1 150 grams (1 mol) of 4-tertiary-butyl phenol and 192 grams (1 mol) of a 42 per cent aqueous 10 azeotrope of ethylene chlorohydrin were mixed together and 133 grams ofa 30 per cent aqueous sodium hydroxide solution addedthereto over a period of one hour at temperatures gradually increasing from to 42 C. Stin'ing was main- 15 tained for an additional hour after which the reaction batch was allowed to stand for 16 hours at room temperature. An oily layer separated therefrom and was fractionally distilled, whereby 145 grams (0.748 mol) of the beta-hydroxy-ethyl. 20 ether of 4-tertiary-butyl phenol was obtained as a water white oil boiling at 126.5-I27.5 C. at 4 millimeters pressure, freezing at approximately 15 C. and having a specific gravity of 1.015 at 20/4 C. This compound was substantially in- 5 soluble in water but somewhat soluble in most' organic solvents. Example 2 1 mol of 4-tertiary-amyl phenol, 1 mol of sodium hydroxide, and 2.5 mols of water were mixed together and 192 grams of a 42 per cent aqueous azeotrope of ethylene chlorohydrin reacted therewith substantially as described above. Theresulting oily layer was fractionated, whereby there was obtained 0.35 mol of the beta-hydroxy-ethyl other of 4-tertiary-amyl phenol. This compound is a water white liquid boiling at 145-148 C. at 4 millimeters pressure, and having a specific gravity of 1.0045 at 20/4 C.

Example 3 1 Example 4 2 mols of 4-tertiary-butyl phenol, 2 mols of sodium hydroxide, and 400 milliliters of water were mixed-together, and 2 mole of propylene chlorohydrmintheiosmoialilpercentaqucous sssotropsgradually addsdthereto overs period oi2hoursandattemperaturesgraduallyincreasingirom'lfl C.to96. C. 'Ihereaction mixture .wss refluxed ior a short time after the addition oi the chlorohydrincooled, acidified, and the resulting oil separated therefrom. The latter was washed with water and distilled whereby there was obtained 1.4 mole oi the hydroxy-propyl ether 01' i-tertiary-butyl phenolas a white crystalline solid, melting at 45 0., and boiling at IMP-155 C. at 10 millimeters pressure.

Other compounds prepared in a similar manner include the iollowing:

Beta-hydroxy-ethyl ether oi 2-chloro-4-tertl' ary-butyl phenol, a water white liquid boiling at 130-132 C. at 2 millimeters pressure, and having a specific gravity of 1.121 at /4 0.; Beta-hydroxy-ethyl ether oi Z-methyl-i-tertiary-butyi phenol, a white crystalline solid melting at 38' 0.. and boiling at 130-132 C. at 3 millimeters pressure;

Beta-hydroxy-ethyl ether of 2,4-di-tertiarybutyl-B-chlorophenol, a thick viscous liquid boiling at USP-154 C. at 2 millimeters pressure, and

" having a specific gravity of 1.072 at cove" 0.

. i-tertiary-butyl-fi chloro-phenol; beta-hydroxyethyl ether oi- 2-methyl-4-tertiary-butyl-6-bromo-phenol; beta-hydroxy-ethyl ether oi 2-n-pro: pyl4-tertiary-butyl phenol; beta-hydroxy-ethyl ether oi 2-methyl-4,6-ditertlary-butyl phenol; beta-hydron-ethyleether oi 2-bromo-4-tertiaryamyl phenol; beta-hydroxy-ethyl ether of 2,6-dlbromo-i-tertiary-amyl phenol; beta-hydroxyethyl ether oi 2,6-dichloro-4-tertiary-amyl phenol; beta-hydroxy-ethyl ether oi -2-bromo-(lchloro-i-tertiary-amyl phenol; beta-hydroxyethyl ether of 2-methyl-4-tertiary-amyl-6-chloro-phenol; beta-hydroxy-ethyl ether of 2-me-- thyl-i-tertiary-amyl-fi-bromo-phenol; beta-hydroxy-ethyl ether oi 2,4-diterti -amyl-phenol; beta-hydroxy-ethyl ether oi 2, tertiary-amyl- B-ohloro-phenol; beta-hydroxy-ethyl ether oi 4- tertiary-hexyl phenol; beta-hydroxy-ethyl ether oi 2-bromo 4-tertiary-hexyl phenol; betahydroxy-ethyl ether of 2,6-dichloro-4-tertiaryheptyl phenol; beta-hydroxy-ethyl ether oi 2- chloro-i-tertiary-heptyl phenol; beta-hydroxyethyl ether of 2-chloro-4-tertiary-octyl phenol; beta-hydroxy-ethyl ether of 2,6-dibromo-4-tertiary-octyl phenol; beta-hydroxy-ethyl ether oi 2-meth'yl-4-tertiary-octyl phenol; beta-hydroxyethyl ether oi 2-'nepropyl-4-tertiary-octyl phenol; beta-hydroxy-ethyl ether oi 2-,methylt-tertiary-octyl-G-bromo-phenol; hydroxypropyl ether oi 2,4-ditertlary-butyl-Bemethyl phenol; hydroxy-m'opri ether of i-tertiary-amyl phenol; hydroiw-propyl ether oi 2-bromo-4-tertiary-amyl phenol; hydroxy propyl ether of 2-chloro-4-tertiary amyl phenol; hydroxy-propyl ether oi 2,4- ditertiary-aml-8-methyl phenol; hydroxy-propyl ether oi 2,4-ditertiary-amyl-8-bromo-pheno1; hydroxy-propyl ether oi 2-n-propyl-4-tertiaryamyl phenol; hydroxy-propyl ether oi i-tertiaryaisaess heal phenol; hydroxy-propyl ether oi 4-tertiaryheptyl phenol; hydroxy-pr p i ether oi z-bromo- 'i-tertiary-octyl phenol; hydroxy-propyl ether of i-tertiary-octyl phenol; hydroxy-propyl ether of 2,6-dichloro-4-tertiary-octyl phenol; hydroxypropyl ether oi 2-ohloro-4-tertiary-octyl-8- bromo-phenol; hydroxy-propyl ether oi x2- methyl-i-tertiary-octyl-B-chloto-phenol; hydroxy-propyl ether oi 2,8-dimethyl-4-te'rtiaryoctyl phenol etc.

Certain oi the" compounds described in the ioregoing examples have been tested by the Peet- Grady meth (Soap, 8, No. 4,1932) and iound to be particul 1y valuable as fly spray toxics. For example, a 3 per cent solution of beta-hydroxyethyl ether of i-tertiary-butyl phenol in kerosene, when tested against houseilies, was iound to give in excess of a 90 per cent knock-down and an average kill of over 45 per cent in 24. hours. A 5 per cent kerosene solution of beta-hydroxy-ethyl ether of i-tertiary-octyl phenol killed 19.7 per cent oi houseflies contacted therewith when tested in a similar manner.

This application is a continuationin part of our co-pending application Serial No. 126,810, filed February 20, 1937.

Other modes oi applying the principle oi our invention may be employed instead of those explained, change being made as regards the materials employed provided the products described in the following claims be thereby obtained.

We, thereiore, particularly point out and distinctly claim as our invention:

1. A compound having the formula wherein one B represents hydrogen, the other R represents a member of the group consisting of methyl and hydrogen, X represents a tertiaryallryl radical containing not more than 5 carbon atoms, and Y represents halogen.

3. A compound having the iormula wherein one It represents hydrogen, the other 3 a,1ss,oss

represents a member of the group consisting of methyl and hydrogen, 1: represents'a tertiaryalkyl group containing not more than 5 carbon atoms, one Y represents chlorine, and the other Y represents a member or the group consisting oi chlorine and hydrogen.

4. A compound having the iormula wherein one R represents hydrogen, the other R represents a member of the group consisting of methyl and hydrogen, X represents a tertiaryalkyl radical containing not more than 5 carbon atoms, and Y represents chlorine.

5. A compound having the formula wherein one.R represents hydrogen, the other It represents a member of the group consisting of methyl and hydrogen, one Y represents chlorine, and the other Y represents a member of the group consisting of chlorine and hydrogen.

'1. A compound having the formula x represents a tertiaryalkylradical containing not more than 5 carbon atoms, one Y represents halogen, and the other Y represents a member of the group consisting oi. halogen and hydrogen.

8. A compound having the formula wherein x represents a tertiary-alkyl radical containing not more than 5 carbon atoms, one Y represents chlorine, and the other Y represents a member or the group consisting of chlorine and hydrogen.

9. A compound having the formula CHa- -03:

wherein one Y represents halogen, and the other Y represents a member of the group consisting of halogen and hydrogen.

10. A compound having the formula o-cm-cm-on CH:- -CHs H! wherein one'Y represents chlorine and the other I Y represents a member of the group consisting of chlorine and hydrogen.

11. A compound having the formula wherein one R represents hydrogen, and the other R represents a member of the group consisting of the methyl radical and hydrogen.

GERALD H. COLEMAN. JOHN W. ZEMBA. 

